Patent GB-1120304-A (GB)
Title: Polycationically active polymers and their production
Inventor: SMITH SMAUEL
IPC: C08G63/91
Filed: 1966-02-23
Abstract: The invention comprises polymers which are cationically active at at least two ends, said activity being characterized by said polymer's ability (a) to react with at least a two-fold molar excess of ammonia at a temperature below 25 DEG C. to produce polymeric polyprimary amines or polyamides in which the amine or amide groups are in terminal positions, and (b) to initiate the polymerization of tetrahydrofuran monomer at 25 DEG C.  Suitable polymers include polyethers which may be derived from alkylene oxides, sym-trioxane and especially tetrahydrofuran, polyesters, polythioesters, polyols, polythiols, polycarboxylic and polysulphonic acids, polyamides, polythioethers and vinyl polymers and these may be made cationically active by one of two methods.  A direct method involves polymerizing at least one cationically polymerizable cyclic ether monomer which is predominantly tetrahydrofuran or sym-trioxane, in a polymerization media which is substantially free of chain terminating agents and which contains catalysts such as (FSO2)2O, (CF3SO2)2O, Cl2O7, FSO2-O-O2SCF3, FSO2F.PF5, CF3SO2F.SbF5, CF3SO2Cl.SbCl5 and ClO3F.BF3. Other catalysts mentioned include 1,4-butane - bis - (fluorosulphonate), 1,4 - butane-bis - (trifluoromethane sulphonate) and the corresponding esters of poly-(tetramethylene) glycol.  An indirect method comprises reacting a prepolymer having at least two terminal radicals selected from the group consisting of hydroxyl, thiol, alkali metal alkoxide or mercaptide, carboxylic acid and sulphonic acid with catalysts such as FSO3H, (FSO2)2O, FSO3C4H8-O3SF, CF3SO3H, (CF3SO2)2O, CF3SO2Cl, CF3SO3(C4H8O)2O2SCF3, HClO4, Cl2O7 and ClO4-C4H8-O4Cl. The terminally polycationically active polymers may also be prepared by reacting a polymer having as the terminal radicals either acyl bromide or acyl chloride with (a) a protonic acid which is stronger than 100% sulphuric acid and which is capable of effecting the cationic polymerization of tetrahydrofuran without chain transfer or (b) a salt thereof.  Examples of reactants (a) or (b) include FSO3Ag, CF3SO3H, CF3SO3Ag, HClO4 and AgClO4. The polycationically active polymers are effective alkylating or acylating agents and may be reacted with inorganic and organic compounds containing active hydrogen to give linear and cross-linked polymers.  Many metal salts react with the polycationically active polymers to effect a double decomposition reaction.  Aromatic compounds capable of undergoing a FriedelCrafts reaction may also be ring alkylated or acylated using the cationically active polymers. Aromatic compounds, particularly phenolic compounds, which have been alkylated or acylated with the cationically active polymers may be used to obtain flexible resins, e.g. phenolic resins, epoxy resins, polycarbonate resins and amino aldehyde resins and can also be used as intermediates in the organic syntheses of dyes and drugs. The cationically active polymers are also useful as intermediates in graft or block copolymerization reactions. In Example (2E) an amine-terminated poly-(tetrahydrofuran) is prepared and used to cure an epoxy resin, and to react with methylene bis-(4-phenylisocyanate) to form an elastomer. In Example (6) an isocyanate-terminated poly (THF) is prepared and reacted with hexamethylene diamine to give a polyurea.  In Example 11 a hydroxy-terminated polybutylene adipate is treated with trifluoromethane sulphonic anhydride then with LiBr or, in Example (12), with tetrahydrofuran then LiBr.  Uses.-Plastic and protective coating compositions, elastomers, polymeric surface-active agents, impregnants, binders, potting compositions, adhesives, fibres, tape backings, foams and films.